TOF MS indicating only one predominant structure, i.e. 4. For
example, the peaks at m/z 1319.0 and 1419.2 correspond to
lithium adducts of 4 where x = 10 and 11 respectively,
now observed at m/z 1423.0 and 1522.8 for x = 10 and 11,
calculated m/z 1422.3 and 1522.4; this reaction is quantitative
and no peaks from residual 4 are observed. When the reaction is
carried out at a higher MMA: 3 ratio for 120 min a higher
n
calculated m/z 1318.3 and 1418.4. Control over M and PDI is
obviously not affected detrimentally by the presence of the
primary alcohol group present in the initiator, which might have
been expected to complicate the reaction by coordination to the
copper catalyst. Indeed the PDI is narrower and the rate of
polymerisation faster with 3 than that obtained using a non-
functional initiator. Thus ATRP with 1 as catalyst can be
utilised to give PMMA of structure 4 as the only detectable
product under these conditions. The hydroxy group can be
further reacted with benzoyl chloride to give 5 quantitatively.
molecular weight polymer is produced, Mn
PDI = 1.22, as expected (reactions B and C). Again analysis
shows terminal hydroxy functionality.
Living or pseudo-living polymerisations have a low rate of
termination relative to rate of propagation. This is demonstrated
by following a reaction with time (reactions D–K; L is the final
product from this reaction). Fig. 3 shows that M increases
n
linearly with conversion, up to approx. 80%, whilst PDI remains
narrow for reaction with MMA: 3 = 200. In this case the
expected M (theory) at 100% conversion = [100/1 3 100.14
n
=
4540,
1
The terminal benzoyl group of 5 is observed by H NMR,
Fig. 1(c), and is detected by SEC with UV detection at 200 nm,
(mass of MMA)] + 220 (mass of end groups) = 20248. The
PDI is broader than would be expected for a true living
polymerisation with fast initiation (theoretically 1 + 1/DP).
However, PDI does not increase with increasing conversion as
would be expected for a reaction with significant termination
and this is most probably due to slow initiation relative to
propagation.9
4
shows no absorption at this wavelength. MALDI-TOF MS
shows a new series of peaks corresponding to 5, e.g. peaks are
1319.0
100
90
80
70
60
50
40
30
20
10
0
In summary, atom transfer radical polymerisation with 1 as
catalyst and 3 as initiator leads to a-hydroxy functional PMMA.
The presence of the hydroxy group during the polymerisation
does not reduce the control over the polymerisation, and a
1
219.0
1
419.2
n
narrow PDI polymer with controlled M is obtained.
1119.4
We thank the EPSRC (C. W. GR/K65652, C. B. J. GR/
K04606, A. J. S. CASE award) and Courtaulds for funding. We
also thank the late Dr Andrew McCamley who proved a source
of inspiration and ideas during this work.
Footnotes
†
‡
E-mail: msrgs@csv.warwick.ac.uk
0.25 g of red phosphorus (8.06 3 10 mol) were added to 35.4 ml (0.338
2
3
mol) of isobutyryl chloride. The mixture was placed under gentle reflux and
0 ml of bromine (0.388 mol) were added slowly over 8 h. The mixture was
2
refluxed for a further 4 h and the crude reaction mixture added slowly to 350
ml of anhydrous ethylene glycol (6.27 mol). The reaction mixture was
refluxed for 4 h, filtered into 500 ml of distilled water and the product
extracted into chloroform. After washing with water and sodium hydrogen
carbonate and drying over magnesium sulfate the product was isolated as a
1
200
1300
1400
Mass / charge
colourless liquid after the removal of solvent and vacuum distillation at
1
6
4.5 °C and 0.1 Torr. H NMR (CDCl
3
, 373 K, 250.13 MHz) d 4.30 (t, J 9.6
Fig. 2 Partial MALDI-TOF MS of 3 between x = 8 and 11, peaks
correspond to lithium adducts of molecular ions with no observable
fragmentation
13
1
Hz, 2 H), 3.85 (t, J 9.6 Hz, 2 H), 1.94 (s, 6 H): C{ H} NMR (CDCl
K, 100.6 MHz) d 171.83, 67.30, 60.70, 55.72, 30.59. IR (NaCl, film) 3436
br), 2977, 1736 (s), 1464, 1391, 1372, 1278, 1168, 1112, 1080, 1023, 950,
3
, 373
(
6
§
44. EI MS: 213, 211 (mass peaks), 169. 167, 151, 149, 123, 121.
Typical polymerisation procedure. 0.1376 of copper(i) bromide (98%, 9.6
2
3
10 4 mol) were added to 40 ml of xylene and 20 ml of methyl
2
3
methacrylate (0.187 mol). 0.4272 g of 2 (2.89 3 10 mol) were added and
20000
the mixture deoxygenated by one freeze-pump-thaw cycle prior to the
2
4
addition of 0.2029 g of 3 (9.61 3 10 mol) at room temperature. The deep
red solution was heated at 90 °C for 70 min. The final product was isolated
by precipitation into hexanes.
1
�5 000
References
1
M. Kato, M. Kamigaito, M. Sawamoto, and T. Higashimura, Macromole-
cules, 1995, 28, 1721.
10000
M
2 K. Matyjaszewski and J.-S. Wang, Macromolecules, 1995, 28, 7901.
3
K. Matyjaszewski, 2nd IUPAC Symp. Free Radical Polym. Kinetics and
Mechanism, Preprints, 1996, 22.
4
V. Perced, B. Barboui, A. Neumann, J. C. Ronda and M. Zhao,
Macromolecules, 1996, 29, 3665.
5000
5
6
7
V. Percec and B. Barboui, Macromolecules, 1995, 28, 7970.
D. Bellus, Pure Appl. Chem., 1985, 1827.
C. Granel, P. Dubois, R. Jerone, P. Teyssie, Macromolecules, 1996, 29,
8
576.
0
8
9
D. M. Haddleton, C. B. Jasieczek, M. J. Hannon and A. J. Shooter,
Macromolecules, in the press.
K. Matyjaszewski, J. Phys. Org. Chem., 1995, 197, 8.
0
10 20 30 40 50 60 70 80 90 100
Conversion (%)
n
Fig. 3 Plot showing how M from SEC increases with conversion for
experiments D–K
Received, 29th January 1997; Com. 7/00677B
684
Chem. Commun., 1997